Bis carbonyl dithiophosphate compounds



Patented Nov. 13,1951

BIS CARBONYL DITHIOPHOSPHATE COMPOUNDS Arthur H. Fischer, New York, N.Y., assignor to Minerec Corporation, New York, N. Y.

No Drawing. Original application June 26, 1946, SerialNo. 679,566.Divided and this application May 9,1947, Serial No. 747,143

3 Claims. 1

This invention relates to the production of new organic compounds andhas for an object the provision of new dicarbonyl compounds. Morespecifically, the invention contemplates the provision of dicarbonylcompounds comprising organic dith-io acid radicals and dicar-bonylcompounds in which the carbonyl groups are joined together by means ofmultivalent organic radicals. The invention further contemplates theprovision of dicarbonyl compounds comprising xanthate radicals anddithiophosph-ate radicals. Compounds of the invention include dicarbonyicompounds in which the carbonyl groups are joined together by ycolradicals such, for example, as OC2H4--O and compounds such for example,as derivatives of ethylene glycol and diethylene glycol.

A dicarbonyl compound comprising a xanthate radical may be produced, forexample, by reacting a salt or an acid comprising a xanthate radicalwith a dihaloformate to form a product having the following structuralformula:

OR on" i t t i in which Y is a multivalent organic radical such, forexample, as a glycol radical, and R and R are organic radicals such, forexample, as ethyl radicals. I

A dicarbonyl compound comprising a dithiophosphate radical may beproduced, for example, by reacting a salt or an acid comprising anorganic dithiophosphate radical with a dihaloformate to form a producthaving the following structural formula:

in which Y is a multivalent organic radical such, for example, as aglycol radical, and R, R", R' and R"" are organic radicals such, forexample, as ethyl radicals.

When substitution products of organic dithio acids containing organicradicals are employed, bis carbonyl dithio compounds containingcorresponding organic radicals will be produced. Substitution productsof acids and salts containing alkyl radicals or aryl radicals or bothmay be employed, and, in the above formulae, R, J, R' and R" representsuch radicals.

The use of (ii-substituted organic compounds comprising dithiophosphateradicals results in the production of tetra-substituted compounds.

The use of (ii-substituted esters, for example, results in theproduction of tetra esters of bis carbonyl dithiophosphate compounds.

The use of xanthates results in the production of bis carbonyl xanthatecompounds containing the organic radicals or groups present in thereagents employed.

In producing compounds in accordance with the invention, substitutionproducts of acids and salts cointaining alkyl radicals or aryl radicalsor both may be employed.

The compounds of the invention are suitable for various uses, and theymay be employed with rarticular advantage as mineral collecting agentsin the concentration of minerals by froth flotation.

Among the compounds found most suitable for use in fiuotationconcentration processes are COMPOUND A O H s Dicthylrne glycol biscarbonyl'ethyl xanthate COMPOUND c A reaction product of sodium diethyldithiophosphate and diethylene glycol chloroformate having the followingstructural formula:

Diethylene glycol bis carbonyl diethyl dithiophosphate COMPOUND D Areaction product of sodium butyl xanthate and diethylene glycolchloroformate having the following structural formula:

Diethylene glycol bis carbonyl butyl xanthate stirrer The use of thecompounds of the invention for the concentration of minerals isdescribed and claimed in my copending application Serial No. 679,565,filed June 26, 1946, now Patent No. 2,501,269.

The following examples illustrate methods of preparing compounds inaccordance with my invention suitable for use in the flotation methodsor processes of my invention:

Example I Preparation of the reaction product of sodium ethyl xanthateand diethylene glycol chloroformate.

g o o s 300 grams of pure sodium ethyl xanthateZHzO (13% in excess oftheory) were dissolved in 1 liter of water in a 2 liter flask providedwith and thermometer. 170.4 grams of diethylene glycol chloroformatewere added to this solution over a period of fifteen minutes. Thetemperature of the reaction mixture rose slowly to 30 C. The mixture washeated to 45 C. The heating was then discontinued and the temperatureslowly fell to that of the room. The total time of reaction was fivehours.

The oily product was separated and the aqueous layer extracted withcarbon bisulfide.

The oily product and the carbon bisulfide extracts were combined and thecarbon bisulfide was distilled off in vacuo.

The product was a yellow oil. The yield was 241 grams which is 81.17% ofthe theoretical amount for the above equation.

Analysis: Per cent Sulfur calculated 31.86

Sulfur found 31.41

Example II Preparation of the reaction product of sodium diethyldithiophosphate and ethylene glycol chloroformate:

s y) o s mixture, contained in a 1 liter flask provided with a stirrerand thermometer, was stirred for fifteen minutes after the addition ofthe sodium carbonate, to complete the neutralization. 73 grams ofethylene glycol chloroformate were then added in 20 minutes, thetemperature was kept below 25 C. by means of a cooling bath, and thestirring was continued for two hours after the ethylene glycolchloroformate had been added.

The reaction mixture was diluted with water and the water insoluble oilyreaction product was separated and dried by warming to C. in

vacuo.

191 grams of product were obtained which is a theoretical yield.

Analysis: Per cent Sulfur calculated 26.36 Sulfur found 26.35

Dicarbonyl compounds containing other organic radicals may be producedby the same procedure or by similar procedures when employing organicreagents containing such other organic radicals.

This application is a division of my application Serial No. 679,566,filed June 26, 1946, wherein I have claimed the xanthate compoundsdescribed herein.

I claim: 1. A compound having the structural formula:

OR! 0R1! OR!!! ORIIH I;S(H}-O-C2H4OCSfi s o s in which R, R", R and R.""are ethyl radicals.

2. A compound having the structural formula:

in which R, R", R' and R" are ethyl radicals and X is a residue fromanethylene lycol having a formula from the group -OCzH4O-- and-OC2H4OC2H4O-.

3. A compound having the structural formula:

fiS?OCzHlOC2H4O-CS S in which R, R, R and R" are ethyl radicals.

ARTHUR, H. FISCHER.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 1,949,629 Romieux et al Mar. 6,1934 2,434,357 Fischer Jan. 13, 1948

2. A COMPOUND HAVING THE STRUCTURAL FORMULA: